Fuel composition for a diesel engine

ABSTRACT

The invention is directed to a fuel composition for diesel engines. The fuel composition comprises 0.1-99% by weight of a component or a mixture of components produced from biological raw material originating from plants and/or animals and/or fish. The fuel composition comprises 0-20% of components containing oxygen. Both components are mixed with diesel components based on crude oil and/or fractions from Fischer-Tropsch process.

This application is a continuation of application Ser. No. 16/891,203,filed Jun. 3, 2020, now U.S. Pat. No. 10,941,349, which is a divisionalof application Ser. No. 14/033,134, filed Sep. 20, 2013, now U.S. Pat.No. 10,723,955, which is a continuation of application Ser. No.13/480,562, filed May 25, 2012, now abandoned, which is a continuationof application Ser. No. 12/354,634, filed Jan. 15, 2009, now U.S. Pat.No. 8,187,344, which is a divisional of application Ser. No. 11/852,096,filed on Sep. 7, 2007, now abandoned, which is a continuation ofapplication Ser. No. 10/655,798, filed on Sep. 5, 2003, now U.S. Pat.No. 7,279,018, which claims the benefit of priority of U.S. ProvisionalApplication No. 60/408,302, filed on Sep. 6, 2002. The entire content ofeach application is hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a fuel composition for diesel engines,comprising components based on vegetable oil and/or animal fat and/orfish oil, diesel components based on crude oil and/or fractions fromFischer-Tropsch process, and optionally components containing oxygen.

PRIOR ART

Currently used fuels for diesel engines mainly contain components fromcrude oil. The aim of the climate agreement of Kyoto is to eliminatedetrimental influences due to human activities on the atmosphere, andthus on the climate. The EU has agreed on reducing emissions of carbondioxide, methane and other greenhouse gases by eight percent until 2010,starting from the levels of 1990. One of the objects of the EUagricultural policy is to find uses for agricultural overproduction, andto increase the self-sufficiency for fuels. Accordingly, an EU directiveis being prepared, demanding that at least two percent of the petrol anddiesel fuel consumed in 2005 should be of biological origin. It isanticipated that one of the requirements of this directive is toincrease the proportion of biocomponents to about six percent until2010. The directive will be validated in all EU countries in the nearfuture.

At the moment, the most common component of biological origin in fuelsis rapeseed oil methyl ester, referred to as RME. RME is either used assuch or as a mixture with fuels. Drawbacks of RME are its poormiscibility with diesel fuels, and, in comparison to a conventionaldiesel fuel (EN 590), particularly under low temperature conditions, itspoor storage stability and poor performance at low temperatures.Moreover, it causes engine fouling and increases emissions of nitrogenoxides (NOx). A by-product of the production process of RME is glycerol,which may become a problem when high amounts of the product areproduced—Esters of other vegetable oils may be produced in similarmanner, and methyl esters of fatty acids are generally known as FAMEs(fatty acid methyl ester). These FAMEs may be used in similarapplications as the rapeseed oil methyl ester, but they also have anegative effect on the quality of the diesel fuel, particularly withrespect to the performance thereof at low temperatures, and in addition,the use thereof in fuels increases the emissions of nitrogen oxides. Insome cases FAME and RME cause higher particle emissions and smokedevelopment of the cold driven engine.

Vegetable oils and animal fats may be processed to decompose the esterand/or fatty acid structure and to saturate the double bonds of thehydrocarbon chains, thus obtaining about 80 to 85% of n-paraffin productrelative to the mass of the starting material. This product may bedirectly mixed with a diesel fuel, but a problem with the fuel soproduced is its poor performance at low temperatures. In addition,n-paraffins having a carbon number of fatty acids are waxy with a highsolidification point, typically above +10° C., thus limiting the use ofthese compounds in diesel fuels at least at low temperatures.

WO 2001049812 discloses a method for producing a diesel fuel with amolar ratio of isoparaffins to n-paraffins of at least 21:1. In themethod, a feed stock containing at least 50% of C10-paraffins iscontacted with a catalyst in the isomerization reaction zone.

WO 2001012581 discloses a method for producing methyl esters useful asbiological diesel fuel, wherein mixtures of fatty acids andtriglycerides are esterified in one phase. In this method, a solution isformed from fatty acids, triglycerides, alcohol, acid catalyst andco-solvents at a temperature below the boiling point of the solution. Aco-solvent is used in amounts to provide a single phase, then thesolution is maintained for a period of time sufficient for the acidcatalyzed esterification of the fatty acids to take place. Thereafter,the acid catalyst is neutralized, a base catalyst is added totransesterify the triglycerides, and finally, the esters are separatedfrom the solution. Thus a biofuel containing esters is obtained, havinga glycerol content of less than 0.4% by weight

U.S. Pat. No. 6,174,501 presents a method for producing oxidized dieselfuel of biological origin. This oxidized biological diesel fuelcomprises a mixture of transesterified triglycerides.

FI 100248 describes a two-step process for producing middle distillatefrom vegetable oil by hydrogenating fatty acids of the vegetable oil, ortriglycerides, to give n-paraffins, and then by isomerizing then-paraffins to give branched-chain paraffin—Any gases, liquid dropletsand solid particles present in the atmosphere in amounts being hazardousto human health and/or having a detrimental effect on animals, plantsand different materials, are considered as air pollutants. Air pollutionmainly originates from three main emission sources, i.e., the industry,energy production, and traffic.

The harmfulness of particle emissions is caused by the substances andcompounds they carry, such as heavy metals and other carcinogenic andmutagenic compounds. Particles present in exhaust gases are small andthus hazardous to health.

Greenhouse gases allow for the penetration of the radiation from the sunto reach the earth, preventing, however, the thermal radiation fromescaping from the earth back to space. They thus contribute to thewarming of the earth. One of the most significant greenhouse gases iscarbon dioxide released, for instance, during the combustion of fossilfuels.

Nitrogen oxides are acidifying compounds. This acidification may, forinstance, lead to plant damages and species changes in surface waters.Nitrogen oxides may also react with oxygen to give ozone. Thisphenomenon contributes particularly to air quality in cities.

As the above teachings indicate, there is a need for a high quality fuelcomposition for diesel engines containing components of biologicalorigin and also meeting the quality requirements for diesel fuels underlow temperature operation conditions. Moreover, the fuel should be moreenvironmentally friendly than prior art solutions.

GENERAL DESCRIPTION OF THE INVENTION

The object of the invention is to provide a more environmentallyfriendly fuel composition for diesel engines containing components ofbiological origin, and also meeting the quality requirements for dieselfuels under low temperature conditions.

The fuel composition for diesel engines of the invention, containingcomponents of biological origin, comprises at least one componentproduced from a biological starting material obtained from plants,animals or fish, diesel components based on crude oil and/or fractionsfrom Fischer-Tropsch process, and optionally components containingoxygen.

The characteristic features of the fuel composition for diesel enginescontaining components of biological origin are presented in the appendedclaims.

DETAILED DESCRIPTION A OF THE INVENTION

It was surprisingly found that the diesel fuel composition of theinvention, containing components of biological origin, also meets thequality requirements for diesel fuels under low temperature conditions.The composition of the diesel fuel of the invention comprises thefollowing:

a) 0.1 to 99% by volume, preferably 0.1 to 80% by volume of a componentor a mixture of components produced from biological raw materialoriginating from plants and/or animals and/or fish;

b) 0 to 20% by volume of components containing oxygen selected from thegroup consisting of aliphatic alcohols such as methanol and ethanol,ethers, fatty acid esters such as methyl and ethyl esters, water, andmixtures containing the same; both components a) and b) being mixed asan emulsion or dissolved in diesel components based on crude oil and/orfractions from Fischer-Tropsch process.

Component a) produced from biological raw material originating fromplants and/or animals and/or fish, referred to as the biologicalcomponent in the present specification, is obtained by hydrogenating anddecomposing fatty acids and/or fatty acid esters to give a hydrocarbonhaving a carbon number of 6-24, typically n-paraffin as the producthaving a carbon number of 12-24, and optionally by isomerizing thehydrocarbon, typically n-paraffin, thus obtained to give isoparaffin.The hydrocarbon is preferably isomerized.

The biological raw material originating from plants and/or animalsand/or fish is selected from the group consisting of vegetable oils,animal fats, fish oils and mixtures thereof containing fatty acidsand/or fatty acid esters. Examples of suitable materials are wood-basedand other plant-based fats and oils such as rapeseed oil, colza oil,canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, oliveoil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconutoil, as well as fats contained in plants bred by means of genemanipulation, animal-based fats such as lard, tallow, train oil, andfats contained in milk, as well as recycled fats of the food industryand mixtures of the above.

The basic component of a typical vegetable or animal fat is triglyceridei.e., a triester of glycerol and three fatty acid molecules having thestructure presented in the following formula I:

where RI, R2, and R3 are hydrocarbon chains, and R, R2, and R3 may besaturated or unsaturated C6-C24 alkyl groups. The fatty acid compositionmay vary considerably in biological raw materials of different origin.

n-paraffin, iso-paraffin or mixtures thereof produced from thebiological raw material may be used as a diesel fuel component inaccordance with the properties desired for the diesel fuel. Fractionsfrom Fischer-Tropsch-process typically contain high levels of n-paraffinand, optionally, they may be isomerized either simultaneously during theprocessing of the

component of biological origin or separately therefrom, or they may beused as such.

The biological component may be produced, for instance, with a processcomprising at least two steps and optionally utilizing thecounter-current operation principle. In the first hydrodeoxygenationstep of the process, optionally running counter-current, the structureof the biological raw material is broken, compounds containing oxygen,nitrogen, phosphor and sulphur as well as light hydrocarbons as gas areremoved, and thereafter, olefinic bonds are hydrogenated. In the secondisomerization step of the process, optionally running counter-current,isomerization is carried out to give branched hydrocarbon chains, thusimproving the low temperature properties of the paraffin.

Biological raw material originating from plants, animals or fish andcontaining fatty acids and/or fatty acid esters, selected from vegetableoils, animal fats, fish oils and mixtures thereof, is used as the feedstock.

High quality hydrocarbon component of biological origin, particularlyuseful as a component of a diesel fuel, as an isoparaffinic solvent andas a lamp oil, is ob¬tained as the product having a high cetane numberthat may even be higher than 70. Also, with a turbidity point lower than−30° C. a cetane number higher than 60 can still be achieved. Theprocess can be adjusted according to the desired cetane number andturbidity point.

Advantages of the diesel fuel composition of the present inventioninclude superior performance at low temperatures and an excellent cetanenumber compared to solutions of prior art using FAME-based componentslike RME. Problems associated with the performance at low temperaturesmay be avoided by isomerizing waxy n-paraffins having a carbon numbercomparable with that of fatty acids to give isoparaffins. The propertiesof the products thus obtained are excellent, especially with respect todiesel applications, the n-paraffins typically have cetane numbershigher than 70, and isoparaffins higher than 60, and thus they have animproving effect on the cetane number of the diesel pool, which clearlymakes them more valuable as diesel components. Moreover, the turbiditypoint of the isomerized product may be adjusted to the desired level,for example below −30° C., whereas the corresponding value is about 0°C. for RME and more than +15° C. for n-paraffins. Table 1 below comparesthe properties of an isomerized biological component, RME, and acommercial diesel fuel.

TABLE 1 Density Cetane Turbidity Product (kg/m³) number point (° C.)Isomerized biological component C 800 >60 −30 RME −880 −50 −0 Dieselfuel EN 590 820-845 >51 0 to −15

Fouling of engines is considerably diminished and the noise level isclearly lower when using the diesel fuel composition of the invention incomparison with similar prior art fuels of biological origin containingFAME components, and further, the density of the composition is lower.The composition does not require any modifications of the automobiletechnology or logistics. Higher energy content per unit volume may bementioned as a further advantage compared to RME.

The properties of the diesel fuel composition of biological originaccording to the invention correspond to those of a high quality dieselfuel based on crude oil, it is free of aromates and, in contrast toFAME, it leaves no impurity residues.

Nitrogen oxide emissions due to the fuel composition of the inventionare lower that those from a similar FAME-based product, and further, theparticle emissions are clearly lower, and the carbon portion of theparticles is smaller. These significant improvements in the emissions ofthe fuel composition of biological origin are environmentally veryimportant.

The invention will now be illustrated by means of the following exampleswithout intending to limit the scope thereof.

EXAMPLES Example 1

The following Table 2 compares the emission characteristics of aconventional diesel fuel used in Europe in summer, EN 590 (DI), to thoseof a composition containing 60% by volume of hydrogenated and isomerizedtall oil (TOFA), and 40% by volume of the European summer diesel fuel EN590.

TABLE 2 60% b.v. TOFA + Characteristic Unit 40% b.v. DI DI Turbiditypoint ° C. −15 −8 Cetane number 61.2 55.9 Aromates % b.w. 8.7 19.2 Totalaromates (IP391) % b.v. 9.1 20.0 Polyaromates (1P391) % b.v. 0.8 1.6n-paraffins % b.w. 14_7 24.5 i-paraffins % b.w. 34.2 26.1 Naphtenes %b.w. 42.4 30.2 b.w. = by weight b.v. = by volume

Example 2

Table 3 below compares the emission characteristics of a high qualityreformed crude oil based diesel fuel available on the Finnish market(DITC, produced by Fortum Oyj), to those of compositions containing 30%by volume of hydrogenated and isomerized tall oil (TOFA), and 70% byvolume of DITC, or containing 30% by volume of tall oil methyl ester(MME), and 70% by volume of DITC.

TABLE 3 30% b.v. TOFA 30% b.v. MME Characteristic Unit DITC 70% b.v.DITC 70% b.v. DITC Cetane number 51 57 48 NO, emissions % −1 to −4 +3(compared to DITC) Particles % −3 +22 carbon % −10 to −30 0 to −10 PAH %±0 ±0 Combustion noise decreases ±0 b.v. = by volume

The invention claimed is:
 1. A method for producing an isomerizedbiological component comprising: (1) providing a feed stream of fattyacids having saturated or unsaturated hydrocarbon chains having carbonnumbers within a range of C6-C24, fatty acid esters having saturated orunsaturated hydrocarbon chains having carbon numbers within a range ofC6-C24, or both, derived from at least one biological raw material; (2)hydrodeoxygenating the feed stream to form n-paraffins having carbonnumbers within a range of C6-C24; and (3) isomerizing the n-paraffins toform an isomerized biological component comprising isoparaffins, whereinthe isomerized biological component is suitable for use as a diesel fuelfor a diesel engine and has a cetane number higher than 60 and aturbidity point lower than −30° C.
 2. The method according to claim 1,wherein the biological raw material is chosen from animal-basedmaterial, plant-based material, fish-based material, and mixturesthereof.
 3. The method according to claim 1, wherein the biological rawmaterial is chosen from vegetable oils, animal fats, fish oils, andmixtures thereof.
 4. The method according to claim 1, wherein thebiological raw material is chosen from animal-based fats; fats containedin milk; recycled fats of the food industry; wood-based fats or oils;non-wood, plant-based fats or oils; fats contained in plants bred bymeans of gene manipulation; fish oils; and mixtures thereof.
 5. Themethod according to claim 1, wherein the biological raw material is anon-wood plant based oil chosen from rapeseed oil, colza oil, canolaoil, tall oil, sunflower oil, soybean oil, hempseed oil, olive oil,linseed oil, mustard oil, palm oil, peanut oil, castor oil, and coconutoil.
 6. The method according to claim 1, wherein the biological rawmaterial is an animal-based fat chosen from lard, tallow, and train oil.7. The method according to claim 1, wherein the n-paraffins have carbonnumbers in the range of C12-C24.
 8. The method according to claim 1,wherein the isomerized biological component has a density less than acrude oil based conventional diesel fuel.
 9. The method according toclaim 1, wherein the isomerized biological component has a density lessthan a rapeseed oil methyl ester-based fuel.
 10. The method according toclaim 1, wherein the isomerized biological component leaves no impurityresidues.
 11. The method according to claim 1, wherein the isomerizedbiological component comprises a measurable amount of ¹⁴C.
 12. Themethod according to claim 1, wherein each of the hydrodeoxygenation andisomerization steps is run in a counter-current manner.
 13. A method forproducing a fuel composition, which comprises at least one isomerizedbiological component, comprising: (1) providing a feed stream of fattyacids having saturated or unsaturated hydrocarbon chains having carbonnumbers within a range of C6-C24, fatty acid esters having saturated orunsaturated hydrocarbon chains having carbon numbers within a range ofC6-C24, or both, derived from at least one biological raw material; (2)hydrodeoxygenating the feed stream to form n-paraffins having carbonnumbers within a range of C6-C24; and (3) isomerizing the n-paraffins toform an isomerized biological component comprising isoparaffins, whereinthe isomerized biological component is suitable for use as a diesel fuelfor a diesel engine has a cetane number higher than 60 and a turbiditypoint lower than −30° C.; and (4) forming the fuel composition with theisomerized biological component.
 14. The method of producing a fuelcomposition of claim 13, wherein forming the fuel composition comprisesmixing the isomerized biological component with a diesel component,which is derived from crude oil, fractions from a Fischer-Tropschprocess, or combinations thereof.
 15. The method of producing a fuelcomposition of claim 14, wherein the diesel component is derived fromcrude oil.
 16. The method of producing a fuel composition of claim 15,wherein the fuel composition is 0.1 to 60% by volume isomerizedbiological component.
 17. The method of producing a fuel composition ofclaim 16, wherein the fuel composition has a cetane number higher than60 and a turbidity point lower than −15° C.
 18. The method of producinga fuel composition of claim 13, further comprising a componentcontaining oxygen chosen from aliphatic alcohols, ethers, fatty acidesters, and mixtures containing the same.
 19. The method of producing afuel composition of claim 18, wherein the component containing oxygen isa fatty acid methyl ester.
 20. A method for reducing nitrogen oxideemission of an engine comprising using the fuel composition of claim 15.21. The method according to claim 13, wherein forming the fuelcomposition comprises combining the isomerized biological component witha crude oil-based conventional diesel fuel.
 22. The method according toclaim 13, wherein the fuel composition comprises from 30 to 60% byvolume isomerized biological component.
 23. The method according toclaim 13, wherein the fuel composition has a cetane number higher than60 and a turbidity point less than or equal to −15° C.
 24. An isomerizedbiological component produced by a process comprising: (1) providing afeed stream of fatty acids having saturated or unsaturated hydrocarbonchains having carbon numbers within a range of C6-C24, fatty acid estershaving saturated or unsaturated hydrocarbon chains having carbon numberswithin a range of C6-C24, or both, derived from at least one biologicalraw material; (2) hydrodeoxygenating the feed stream to form n-paraffinshaving carbon numbers within a range of C6-C24; and (3) isomerizing then-paraffins to form an isomerized biological component comprisingisoparaffins, wherein the isomerized biological component is suitablefor use as a diesel fuel for a diesel engine and has a cetane numberhigher than 60 and a turbidity point lower than −30° C.
 25. A fuelcomposition comprising at least one isomerized biological componentproduced by a process comprising: (1) providing a feed stream of fattyacids having saturated or unsaturated hydrocarbon chains having carbonnumbers within a range of C6-C24, fatty acid esters having saturated orunsaturated hydrocarbon chains having carbon numbers within a range ofC6-C24, or both, derived from at least one biological raw material; (2)hydrodeoxygenating the feed stream to form n-paraffins having carbonnumbers within a range of C6-C24; and (3) isomerizing the n-paraffins toform an isomerized biological component comprising isoparaffins, whereinthe isomerized biological component is suitable for use as a diesel fuelfor a diesel engine and has a cetane number higher than 60 and aturbidity point lower than −30° C.
 26. The fuel composition of claim 25,further comprising a diesel component derived from crude oil, fractionsfrom a Fischer-Tropsch process, or combinations thereof.
 27. The fuelcomposition of claim 26, wherein the diesel component is derived fromcrude oil.
 28. The fuel composition of claim 27, wherein the fuelcomposition is 0.1 to 60% by volume isomerized biological component. 29.The fuel composition of claim 28, wherein the fuel composition has acetane number higher than 60 and a turbidity point lower than −15° C.30. The fuel composition of claim 25, further comprising a componentcontaining oxygen chosen from aliphatic alcohols, ethers, fatty acidesters, and mixtures containing the same.
 31. The fuel composition ofclaim 30, wherein the component containing oxygen is a fatty acid methylester.